Textile printing water-in-oil emulsions having as the oil phase a thermoplastic resin plastisol emulsified in a thermosetting resin lacquer



3 the hand of the fabric imprinted, nor does it cause any stiffening or excess Weighting in the printed fabric. When the imprinted fabric is subjected to a subsequent thermal treatment as hereinafter set forth, the imprinted fabric is highly resistant toward fading or discoloration as,

for example, by the loss of pigment due to the effect of washing or laundering operations thereon, or due to the effect which the solvents ordinarily employed in dry cleaning operations may have upon the fabric.

The textile printing compositions of the present invention are pigmented Water-in-oil emulsions in which the continuous or oil phase comprises a lacquer, or a solution of a thermosetting resinous material in organic solvents, said solution having dispersed therein a plastisol of a synthetic thermoplastic resinous material, the organic solvents of the lacquer being substantially- -ing or milling may satisfactorily be carried out in a pony mixer or ball mill, care being taken to avoid undue heating of :the mixture during such `operations since excessive heating tends to cause fusion of the resinous particles of the dispersion. These dispersions can be converted into tough, flexible coatings and self-supporting lms by utilizing any of the standard techniques for forming such coatings and films and by then treating the said dispersion at temperatures sufficient to effect fusion of the dispersed resin particles. Since :the sole dispersion medium of plastisols are non-volatile liquid plasticizers which remain in the coating and lms thus formed, the ratio of plastisol to resin in the original dispersion will, to a large extent, govern :the character of the resultant lm or coating. It has been found that in order to secure the particularly desirable results obtained with the textile printing compositions of the present invention, it is essential that the ratio of plasticizer to resin in the plastisols employed be within certain definite proportions as hereinafter set forth. The resins which have been found to be particularly useful in providing the textile printing compositions of the present invention when employed in the form of plastisols are the polymers of vinyl chloride and the copolymers of vinyl chloride and vinyl acetate.

The most satisfactory binder materials for utilization as the binder material of the oil phase of the emulsions of the present invention are the 'alcoholated melamine-formaldehyde thermosetting resinous condensates which comprise the reaction product of melamine, formaldehyde, and an alcohol, such as butyl alcohol or capryl alcohol, reacted to a point Where the condensate is soluble in organic solvents or in mixtures thereof, such as a. mixture of equal parts of mineral spirits and butyl alcohol. Also suitable for such use are alkyd-modified melamine-formaldehyde thermosetting resinous condensates, as for example, a melamine formaldehyde resinous condensate modified with a drying oil-modified glycerolphthalate resin.

The solvent medium of the oil phase of the printing emulsions of the present invention may comprise any of the ordinary hydrocarbon solvents, both aliphatic and aromatic, and also any of the common terpene solvents, and usually comprises mixtures of these solvents together with certain of the lower aliphatic alcohols since the thermosetting resinous materials mentioned above are usually provided and employed as solutions of the resins in mixtures of either aliphatic or aromatic solvents with various alcohols, such as butanol or capryl alcohol.

The plasticizers employed in preparing :the plastisols or resinous dispersions utilized in the printing compositions of the present invention are Water-immiscible non-volatile liquid organic compounds which are ordinarily miscible with the common organic solvents and thinners employed in the emulsions of the present invention. Examples of such plasticizers include tricresyl phosphate, triphenyl phosphate, dibutyl phthalate, dioctyl phthalate, dibutyl sebacate and dioctyl sebacate. As has been pointed out hereinbefore, the ratio of plasticizer to resin in the plastisols employed in the printing compositions of the present invention should fall within certain definite proportions. For best results, the plastisols utilized in the present invention should have a ratio of plasticizer to resin within the range of from approximately 1 to approximately 2 parts by weight of plasticizer to approximately one part by weight of resin. The use of plasticizer in amounts substantially beyond the limits specified has an adverse effect upon the end results obtained in the nished product. too small an amount of plasticizer resulting in a rather sti' and brittle film of binder and pigment, and too large an amount of plasticizer providing a binder-pigment film which is ltoo soft to prevent rub-off of the pigment particles from the imprinted fabric. Y

As pigment coloring material there may be utilized either dry colors, or dispersed colors; that is, colors wherein the pigment has been dispersed in a solvent suitable for use as a part of the solvent medium of the oil phase of the emulsion. In practicing the present invention, it has been found that the amount of pigment coloring material utilized in the compositions of the present invention should not exceed a ratio of approximately 1.5 parts by weight of pigment to one part by Weight of combined resinous binder; that is, the combined weight of both the thermosetting resinous binder of the lacquer and that of the thermoplastic resinous material incorporated into the compositions of the present invention in the form of a plastisol. Further, the ratio of the vthermoplastic resinous material of the plastisol to the thermosetting resinous binder of the lacquer portion of the oil phase of the printing compositions of the present invention should preferably be maintained within a range of from approximately one to approximately two parts by Weight of the said thermoplastic resinous material to one part by weight of the said thermosetting resinous binder of the lacquer portion of the emulsions` In providing compositions in accordance with the present invention, it has been found to be completely satisfactory and economical to furnish a concentrate which subsequently can be diluted prior to use to furnish a composition with the desired body for the particular operation by `concentrate is prepared..byfemulsifying, as vby which:such 'materials are appliedftofthe fabric.

In- -operations whereA a concentrate f is. furnished the user may dilute-such concentrate.with.v afsui-table. colorless emulsion, until? acompositon. of the. necessaryow properties. .an-d. .containing the amountvv or coloring.` material necessarvior a particular printing- :operation has beenrobtained. Thereafter-such :printing may bei effected Vlay utilization ofI- the equipment ordinarily-employed intextile yprinting operations. When. printing is completed, the .colored fabricfthen. is .treated at elevated. temperatureso-the order of 30u-350 F. for. approximately. .one minutetov effect removal of.: the..volatile. material present vand' to complete `the setting` of' the.. coloringfmaterial upon.l the fabric.

A .colorless Waterainroil emulsion- .(.clear), suitaloleiorv diluting the .pigmentl concentrate -offvthe present invention, is providedasfoll-ows. Aclear i2@ stirring under.y high speed: agitation` conditions, the.Y following material/in` therproportions set iforth.

Eamplcl.

Parts. by weight Drying oil-modified. glycerol-phthalate. resin (40% Iresinsolicls in Vmineralspirits). 70 Xylol 5 Ammonium sulfate 10 Dialyzed waste sulte. liquor rof:v U; S. P.

No. 2,201,812 10 Water 5 The Clear wrwenraiermvsled asEsamnle 1 ifs4 then dilutedv and emulsined with Varsol and water inthe proportionsstt forth, Example 2 to provide a water-inoil emulsion suitalcllev for diluting the .pigment concentrate hereinafter s et forth to the degree of printing consistency `and. shade of color desired,

Example. 2

'Parts.,by. weight ClearV concentrate. of- Example 1 2:5 Varsol 22.5

Water r75.0

ticizersand the vinylresins -offthe` following illustrative examplessof-the-pigment concentra-tes are firstly combined'intoplastisoljform and'then admixed with the remaining )materials-'which constitute the pigment concentrates and the whole is then emulsiedfby suitable means as, for example, by high speed agitation. The organic solvents utilizedr as the solvent medium of the oil-phaseof the :presentn emulsions are substantially non-solvents for,- -the thermoplastic maieials.. 0f the., ,plastisclsfemployei in'- the present inilfintiori.vr However; thefsameisolvents actfasldiluentsicr.themlastisolsf. The plasticzer .u

.component koffthe. =.plast1sois acts-:sm as?l met the.- a resinous -materlall v:tl'lereof: .constitutes :-the dispersant thereof, and as such forms'afstrong attachment for f the.. dispersed :resine` particles; It is believed, that wielen` the .plastisols` are admixed withthe remaining constituents which make :up theemulsions".` off. the vpresent.. invention,- the plastisolsbecome thoroughly; .dispersed Aandi-sus; pended; in.I theV lacquerv vportionlot-the; emulsions ,with the plasticizerfportionofftheplastisol acting las the-suspension medi-umjor the:` iinelyedivilied, dispersed: thermoplastic resinous; particles;`

Illustrative. `examples..of? the.n lpigment concenrtratesofy the present. .inventionf are .-,givenfbelom lar-preparing such, concentrateaA satisfactorilwall or thefmateriak mau-betchargedto anfhighispeed mixer and agitated untilfthe.-reguisitetdispersion andv emulsi-cation is. completed; Toeohtain :the requiredl degree. of. dispersionrwhen. a.. dry color is employedas-thecclcring material of theaemulgsion, the mixture.. `shoulirl' bf2 passedar through; a rollerfmill or -preierablxfzlqeiradmixedfandamilied in arball mill? orfpehblefmll'.

Amvl alcohol- Turpentine Phthalocganine blue pigrne Water YEso'cmbple# -5 1 Partsefbyyweiglit Phthalocyaninegreen=pig ment Water '1%0'20 Eollcwinathenrocedure,hereinhetcre-fautlined, the. pigment 'concentratesoi. theiabpve .illustre tive examples provide, wat Y l e containing---a continuous 'oil p pended'ltherein a dispersionora inelydi'vid d thermoplastic --vresinous material Landkplsjsiciz'e117; YIhese-.emulsionsu mataba dilutedfstany -degree ldesirable with the clear emulsion of Example 2 lto provide the printing compositions of the present invention.

By the use of plastisols of the thermoplastic resinous material herein set forth as part of the oil phase of the pigmented emulsions of the present invention, there are provided printing compositions for textile materials whereby cracking in the nished print is substantially eliminated. Apparently the use of such materials in the form employed in the compositions of the present invention in some manner improves the pigment binding properties of these emulsion systems. Just Why the plastisol dispersion should have such effect upon the nished print may possibly be explained by the fact that since the resinous material of the plastisol is present in the printing composition as a suspension of finely divided vresin particles in the oil phase thereof, upon application of the said printing compositions to textile fabrics as by the conventional printing processes, the thermoplastic resinous material is deposited upon the fabric in the form of nely divided discrete particles interspersed throughout the pigmented thermosetting resinous film. It may be that upon subsequent heat treatment of the imprinted film, the plasticizer present in the imprinted lm acts as a flux whereby the dispersed thermoplastic resin softens and flows together to form a protective film over or about the pigment particles and the thermosetting resinous binder materials which bind the pigment particles to the fabric. However, such explanation is merely theoretical and is not to be construed as a teaching of the actual manner in which the improved pigment binding properties are secured with the compositions of the present invention.

While the above products and processes constitute preferred embodiments of the present invention, changes may be made therein without departing from the scope of the present invention as defined in the appended claims.

What is claimed is:

l. 'A coloring composition for textile materials comprising pigment dispersed in an emulsion containing a discontinuous phase consisting essentially of water, and a continuous oil phase comprising a dispersion in a non-volatile liquid plasticizer of a thermoplastic resinous material selected from the group consisting of a homopolymer of vinyl chloride and a copolymer of vinyl chloride and vinyl acetate, said dispersion being suspended in a lacquer comprising a thermosetting resinous binder selected from the group consisting of alcoholated melamine-formaldehyde resinous condensates and alkyd-modied melamine-formaldehyde resinous condensates in organic solvents which solvents are substantially non-solvents for said dispersed thermoplastic resinous materials, the ratio of plasticizer to said thermoplastic resinous material being within the range of from approximately one to approximately two parts by weight of plasticizer to one part by Weight of said resinous material.

2. A coloring composition for textile materials comprising pigment dispersed in an emulsion containing a discontinuous phase consisting essentially of Water, and a continuous oil phase comprising a dispersion in a non-volatile liquid plasticizer of a homopolymer of vinyl chloride, said dispersion being suspended in a lacquer comprising a thermosetting resinous binder selected `'fromthe group consisting of alcoholated mel- 8 amine-formaldehyde resinous condensates 'and alkyd-modied melamine-formaldehyde resinous condensates in organic solvents which solvents are substantially non-solvents for said dispersed polymer of vinyl chloride, the ratio of plasticizer to said polymer of vinyl chloride being Within the range of from approximately one to approximately two parts by weight of plasticizer to one part by weight of said ploymer of vinyl chloride.

3. A coloring composition for textile material comprising pigment dispersed in an emulsion containing a discontinuous phase consisting essentially of water, and a continuous oil phase comprising a dispersion in a non-volatile liquid plasticizer of a copolymer of vinyl chloride and vinyl acetate, said dispersion being suspended in a lacquer comprising a thermosetting resinous binder selected from the group consisting of alcoholated melamine-formaldehyde resinous condensates and alkyd-modied melamine-formaldehyde resinous condensates in organic solvents which solvents are substantially non-solvents for said dispersed copolymer of vinyl chloride and vinyl acetate, the ratio of plasticizer to said copolymer of vinyl chloride and vinyl acetate being within the range of from approximately one to approximately two parts by weight of plasticizer to one part by weight of said copolymer of vinyl chloride and vinyl acetate.

4. A coloring composition for textile materials according to claim 1 in which the plasticizer is dioctyl phthalate. Y

5. A coloring composition for textile materials according to claim 1 in which the plasticizer is tricresyl phosphate.

6. A coloring composition for textile materials comprising pigment dispersed in an emulsion containing a discontinuous phase consisting essentially of water, and a continuous phase comprising a dispersion in a non-volatile liquid plasticizer of a thermoplastic resinous material selected from the group consisting of a homopolymer of vinyl chloride and a copolymer of vinyl chloride and vinyl acetate, said dispersion being suspended in a lacquer comprising a butylated melamine-formaldehyde resinous condensate in a solvent mixture comprising mineral spirits and butanol, the ratio of plasticizer to said thermoplastic resinous material being Within the range of from approximately 1 to approximately 2 parts by weight of plasticizer to one part by Weight of said resinous material.

'I'. A coloring composition for textile materials comprising pigment dispersed in an emulsion containing a discontinuous phase consisting essentially of Water, and a continuous phase comprising a dispersion in a non-volatile liquid plasticizer of a copolymer of vinyl chloride and vinyl acetate, said dispersion being suspended in a lacquer comprising a butylated melamine-formaldehyde resinous condensate in a solvent mixture comprising mineral spirits and butanol, the ratio of plasticizer to said copolymer of vinyl chloride and vinyl acetate being within the range of from approximately 1 to approximately 2 parts by weight of plasticizer to one part by Weight of said copolymer of vinyl chloride and vinyl acetate.

EDWARD F. ARMATYVS.

References Cited in the file 0f this patent UNITED STATES PATENTS Number Name Date 2,374,602 Kienle Apr. 24, 1945 2,431,078 Powell et al Nov. 18, 1947 2,558,053 Lee June 26, 1951 

1. A COLORING COMPOSITION FOR TEXTILE MATERIALS COMPRISING PIGMENT DISPERSED IN AN EMULSION CONTAINING A DISCONTINUOUS PHASE CONSISTING ESSENTIALLY OF WATER, ADN A CONTINUOUS OIL PHASE COMPRISING A DISPERSION IN A NON-VOLATILE LIQUID PLASTICIZER OF A THERMOPLASTIC RESINOUS MATERIAL SELECTED FROM THE GROUP CONSISTING OF A HOMOPOLYMER OF VINYL CHLORIDE AND A COPOLYMER OF VINYL CHLORIDE AND VINYL ACETATE, SAID DISPERSION BEING SUSPENDED IN A LACQUER COMPRISING A THERMOSETTING RESINOUS BINDER SELECTED FROM THE GROUP CONSISTING OF ALCOHOLATED MELAMINE-FORMALDEHYDE FIED MELAMINE-FORMALDEHYDE RESINOUS CONDENSATES IN ORGANIC SOLVENTS WHICH SOLVENTS ARE SUBSTANTAILLY NON-SOLVENTS FOR SAID DISPERSED THERMOPLASTIC RESINOUS MATERIALS, THE RATIO OF PLASTICIZER TO SAID THERMOPLASTIC RESINOUS MATERIAL BEING WITHIN THE RANGE OF FROM APPROXIMATELY ONE TO APPROXIMATELY TWO PARTS BY WIEGHT OF PLASTICIZER TO ONE PART BY WEIGHT OF SAID RESINOUS MATERIAL. 